Process for the refining of hydrocarbon oil



April 10, 1945.. J. D. DANFORTH PROCESS FOR THE RFINING OF HYDROCARBON OIL Filed Dec. 3l, 1941 m. U1 u v w w H .1n

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Patented Apr. 1o, 194s UNITED STATES PATENT OFFICE v v 2.313.221 PROCESS FOR THE REFINING 0F HYDRO- Y cannon ou.` Joseph D. Daniorth, Chicago, lli.. asaignor to Universa! Oil' Products Company. Chicago, lll.,v a corporation of DelawareI application December s1, 1941, semi No. 425,101

f s claims.4 (ci. isc-ao) This is a continuation-impart 'ofmy copendlng application serial No. avoza. nieu December 16, 1940.

This invention relates to the refining of gasoline and other hydrocarbon distillates to improve the properties thereof. More specifically the invention is concerned with an improved method for treating gasoline wherein the treating action is eilected in a packed reaction zone in the presence of a catalyst or treating agent introduced into the reaction zone by means of a uid carrying medium.

Straight run or cracked gasolines may be treated to reduce the gum and sulfur contents or to improve antiknock and other properties by the use of volatilizable or soluble catalysts or treating agents such as certain volatile halides.-

including aluminum chloride and aluminum bromide. When using treating agents oi' the volatile halide type. the treating process'is preferably conducted in the presence of a hydrogen halide such as hydrogen chloride, and when de` slred, hydrogen may also be present.

In such a treating process it is necessary to have an appreciable quantity `of the treating agent in the reaction'zone.- The treatment is 'active agent are required at any one time, and,

activity or the treating agent. 1t ,will be apparent that my invention minimizes such eiiects.

It, instead o! the iixed-bed operation, a quantity of the treating agent is volatilized and con- -1 tacted with the hydrocarbon oil to be treated.

it is` usually necessary to recycle large amounts of the active agent in order to maintain the necessary quantity oi' treating agent in the reaction zone. l

The process ot the present invention,I avoidsthe recycling ot large amounts of treating agents l when using dissolved or volatillzed treating agents. The reaction zone contains a solid material, usually granular, which may be in the i'orm of a packing, and substantial amounts of treating agent may be gradually and continuously reaction without the disadvantages attendant on the usual ilxed bed operations wherein excessively large amounts of treating agent are contacted with 'the material undergoing reaction.

In one specific embodiment, the present invention comprises a process. for y treatingl gasolinecontaining distillates in the presence of a treatfurthermore. the' catalyst is subject to poisoning or contamination. Even though a large portion ofthe agent may apparently be unchanged, the accumulation of poisons or contaminants is sumcient to reduce the available usefulactivity of the agent to a point which is often below the economical range.

Such a process is almost completely inoperative when oils containing certain highly reactive components are to be treated. For. example, substantial amounts oi oleilnic and/or aromatic hydrocarbons may cause almost complete loss of activity oi' treating agents containing aluminum chloride or bromide when used in the fixed-bed type operation such as has Just been described. 'I'he so-called "lower layer compounds are formed which have little or none of the desired treating activity, Aand these compounds or their chloride treating of hydrocarbons is complicated,

ing agent introduced in refining amounts by means ot a fluid carrying medium into a reaction zone containing a packing material.

The art of treating petroleum hydrocarbon oils and distillates with aluminum chloride is well known in the petroleum industry. The main objects of aluminum chloride treating may be suml marized as follows:

In addition. aluminum chloride treating may result in saturating certain unsaturated compounds present in the distillate and in increasing the percentage of lower boiling components.

It is evident that the chemistry of aluminum and may involve polymerizatiomvcondensation,

decomposition products may mask the remaining u saturation. desulturization, etc. `Moreover;f the aiilnic hydrocarbonsuch as propane or butane may be used as a carrying fluid for introducing the treating agent into-the reaction zone from an outside source. The fluid, which may be in gaseous or liquid form, is passed through a catalyst pickup zone containing the treating agent. This may be disposed in the pickup zone as solid granules of pure halide, as a" liquid, as retained on an adsorbent material, as a binary or ternary mixture with other metal halides, or in any convenient form. The pickup zone is maintained at the pressure and temperature required in order to introduce the desired amount of catalyst or treating agent into the carrying fluid.

The gasoline to be treated may be heated in an independent zone and introduced into the reactionzone containing a solid material, which may be, e. g., in the form of a packing material..

disposed in a tower or chamber.

It may also be advantageous example, at the beginning of a run, to impregnate or coat the packing material with the volatile treating agent so that the treating eilect may be obtained at once without waiting for the agent to accumulate in the treating zone.

The carrying fluid containing the volatile halide is either mixed with the gasoline stream at the inlet to the reaction zone or added to the reaction zone at any convenient point or plurality of points. In this way, the treating agent may be introduced continuously with a portion of the gasoline to be treated. As the active agent in the treating zone becomes spent with use, a further quantity of fresh agent is available because it is being replaced continuously. `In an alternative operation. not necessarily equivalent to this.,thc 'metal halide may be introduced intermittently. y

While I have referred in this specification ,to the use of certain volatilizable" treating agents such as "volatile halides.l it is not intended necessarily that the treating agent be carried in a volatillzed condition to the packed reaction zone. It is true that in many cases when operating with agents such as aluminum chloride (or other halides capable of being volatilized at relatively low temperatures), the conditions of temperature and pressure in the pickup zone are such that the desired amount of treating agent is continuously volatilized and carried into the treating zone by the mechanical entraining action of the stream of carrying fluid. However. under other operating conditions and with other carrying fluids, it appears that the treating agent may actually dissolve in the carrying uid, e. g. when the temperature and pressure in the pick-up zone are so adjusted as to maintain a liquid phase therein. In any event it is not intended that the essential carrying action of the carrying fiuidbe limited to a single mechanism or explanation. The term "volatile halide, therefore, has been used as a in some cases. ior

means of identifying a class of treating agents and not as a. limiting explanation of the operation of the process.

The packing material in the reaction zone may include relatively porous materials. relatively absorptive materials, and others of a less porous or absorptive nature, e. g., porcelain, pumice, firebrlck, quartz, activated charcoal, other activated carbons, diatomaceous earth, kaolin, raw and acid treated clays, silica gel, alumina, magnesia, zirconia. titania, composites of silica with alumina and/or zirconia, and metals possessing considerable surface such as lspongy iron. The solid material should not react to poison or otherwise unduly modify or destroy the treating eflect of the agent.

The alternative reactor packing materials are not necessarily equivalent in their action and the particular packing employed in any given treating process is dependent upon the charging stock being treated, the temperature and pressure employed, the nature of `the treating agent, and

other factors. If desirable, the treating agent and the carrying fluid maybe introduced into the reaction zone at various points between the inlet and exit thereof so that the aluminum chloride is present in the optimum concentration at points shown therein but rather to diagrammatically 4through line 4I2 containing valve I3 to reaction illustrate the general usefulness and advantages of the process. I

-A fluid carrying medium which, for purposes of illustration, may comprise a mixture of hydrogen "ch'loride'and hydrogen is introduced into the system through line I and valve 2 to pump 3. The discharged fluid passes through line 4 containing valve 5, line 6,"and valve 1 to heating coil 8 located in furnace 9. The heated fluid is directed' through line II) to pickup zone II. The temperature and pressure of the carrying fluid in this zone are adjusted to introduce the desired amount of treating agent into the stream. In this case the treating agent contained in zone II may conveniently be aluminum chloride in granular form.

The aluminum chloride-containing fluid passes zone I4. The gasoline to be treated enters line 49 and valve 50 and is pumped by pump 5I through line 52 containing valve 52' to heating coil 53 disposed in furnace 54. The gasoline is discharged through line 46 and passes through valve 4B to line I2 where it is commingled with the aluminum chloride-containing stream at the inlet of reaction zone I4. e

The reaction products leave the reaction zone through line Il and valve I6 and are introduced into a separator I'I. From the bottom of this zone a sludge comprising an aluminum chloride organic complex is continuously removed through line I8 'and valve I9. The remainder of the re' action products is removed overhead through line 20 and discharged through valve 2l into fractionator 22. l If it is desired to operate fractionator ator through line 23, valve 24, pump 25, line 26,

and valve 26'.

Higher boiling material which is 'formed during .the reaction may be removed from the bottom of the fractionator through line 21 and valve 28. Overhead. a stream of gasoline-containing distillate and non-condensable gases is removed through line 3l and valve 32 to condenser 33. The condensate and gases pass through line 34 and valve 35 to receiver 30. The liquidproduct may be removed through -line 31 and valve 38.' The non-condensable gases which in this case contain hydrogen chloride in addition to hydrogen 'and light hydrocarbons are removed through line 38 and valve 40. If desired, however, a portion or all of this gas may be passed through line 4 I valve Y action zone.

42, line 43, and valve 44 into line45. The hydrogen chloride is thus commingled with the gasoline charge and is recycled to the reaction zone. It is also possible `to recycle all or a portion of the hydrogen chloride-containing gases through the pickup zone. In this case the gases pass through line- 4i, valve 42. line 41 and valve 48 into line t where they are commingled with the incoming carrying uld. Si

In certain cases, especially when treating a straight run or highly saturated gasoline, it may be desirable to remove a sidecutfrom the .fraction-- ator and utilize this material `exclusively or as a portion of the uid carrying medium charged to corrosion test. The antiknock properties and color are substantially improved.

Example 2 A thermally cracked gasoline having a bromine number of 65 and containing about 35% unsaturates may be treated with aluminum chloride in a manner similar to Example. l. In this case about mol percent hydrogen and about 10 mol percent hydrogen chloride are present in the re- The aluminum chloride may be picked up with liquefied butane at about 100 Il'. The resulting product has a copper dish gum content of aboutlOmg. with an induction periodof 160 min. which is readily increased by added gum inhibitor and possesses a good color and odor. The susceptibility of the treated gasoline to added tetraethyl lead is substantially increased.

I claim as my invention:

i. In the refining of hydrocarbon oils wherein the oil is passed through a treating zone containing a solid packing material and therein sub- Jected to the refining action of an aluminum i halide.. the improvement which comprises maintaining a bulk supply oi' aluminum halide in a zone apart from said treating zone, passing through and-in relative movement withsaid bulk supply in the second-mentioned zone a gaseous mecomponents of the carrying fluid to theheater and pickup zone. In other cases it may even be desirable to use a portion of the hydrocarbon being treated as the 'carrying duid. Following this procedure, part of the hydrocarbon passes from line 52 through line containing valve I8 into line 4. Here, if desired. it is admixed with other carrying fluids. a

l The operating conditions of my process will depend to a la'rge extent on the nature of the gasoline or distillate being treated. Usually I prefer to use atmospheric or moderate superatmospheric pressures in the reaction zone, but pressures of the order of 200-300 pounds per square inch or more may be used. The temperature in the reaction zone will usually be below about '100 F. However, in many cases of desulfurization or the removal of gum forming constituents I prefer to operate within the range of about F. to

`about 200 F.

The following` examples are given to illustrate the usefulness and 'operability of my process. but in no way do I intend to limit my invention to the specific details therein. 4

Example 1 A straight run gasoline obtained from the distillation of a California crudeand possessing a sulfur content of 0.5% may be= treated according to my process.V A mixture of hydrogen chloride and plant gas comprising essentially hydrogen and methane is used as the fluid carrying medium, and the pickup zone contains granular lumps of aluminum chloride. The reaction zone is packed with crushed firebrick. At atmospheric pressure and a temperature of 120 F. the sulfur content of the gasoline may.. be reduced from 0.5 to 0.02%. The' desulfurized gasoline is nel ative to the doctor test and to the copper strip dium comprising a-hydrogen halide, the gaseous medium being passed `through the-.second-menu tioned zone under conditions such as to pick up in said medium only a portion of said bulk supply of aluminm halide, and introducing the refsultant aluminum halide-containing gaseous medium to said treating zone during the oil renaing operation being performed in the last-named zone. l

2. Iny the refining of hydrocarbon oils ,wherein the oil is passed through a treating zone con taining a solid packing material and therein subiected to the refining action of aluminum chloride. the improvement which comprises maintaining e. bulk supply of aluminum chloride in a zone .apart from said treating zone, passing through and in relative movement with said bulk v supply in thesecond-mentioned zone a gaseous medium comprising hydrogen chloride, the gaseous medium being passed through the secondmentioned zone under conditions such as to pick up in said medium only a portion of said bulk supply of aluminum chloride, and introducing the bulk supply of aluminum halide is vaporized insaid second-mentioned zone and the vapors thereof carried into the treating zone in said gaseous medium.

4. The improvement as defined in claim 2 fur- .ther characterized in that said gaseous medium comprises hydrogen inaddition to the hydrogen chloride.

5. The improvement as defined in claim 1 further characterized in that said gaseous medium contains hydrogen.

' JOSEPH D. DANFORTH. 

